CN1055940A - Antifouling paint compositions - Google Patents
Antifouling paint compositions Download PDFInfo
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- CN1055940A CN1055940A CN 91102406 CN91102406A CN1055940A CN 1055940 A CN1055940 A CN 1055940A CN 91102406 CN91102406 CN 91102406 CN 91102406 A CN91102406 A CN 91102406A CN 1055940 A CN1055940 A CN 1055940A
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- amine
- antifouling paint
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
A kind of antifouling paint compositions contains a kind of marine organisms poisoning agent and comprises a kind of hydrolytic resin as binding agent, and it has at least one following structural formula end group and is undertaken at least one side chain :-X-(O-M-R)
x, X represents in the formula:
Or
Description
The present invention relates to be used in and the pollution of the sea biology, for example belong to surface that animal contacts such as: algae, sea grass and shellfish: the antifouling paint on ship or ship or the power station water coolant water port.This class coating composition generally includes marine organisms poisoning agent and binder polymer.
In recent years, to the existing many suggestions of the self polishing copolymer antifouling paint with binding agent, described binding agent is to contain by discharging the other straight-chain polymer of side with the seawater reaction from polymkeric substance, residual polymkeric substance is eliminated from coating surface, is dispersed or dissolved in fully in the seawater and the fresh layer of exposing a layer binder can similarly be reacted with seawater.As an example, this class coating is disclosed among the GB-A-1457590.The active poisoning agent of paint film sustained release anti-soil of attenuation progressively.The binding agent that commercial effective self-polishing coating adopts only comprises three organotin ester leavings groups.
Disclose a kind of hydrolytic resin and be used in the antifouling paint in EP-A-204458, it comprises that at least one following structural formula end group is undertaken on a kind of resin at least one side chain:
-X-（O-M-R）
x
X represents in the formula:
M be selected from zinc, copper and metal; X is 1 to 2 integer;
R is expressed as and is selected from:
A kind of organic acid and R
1Be the unit price organic group.
EP-A-342276 discloses a kind of method for preparing the metallic resin combination of this class, comprises the mixture reaction that makes A, B and C, wherein:
(A) a kind of resin that contains acid groups;
(B) metal-salt of higher boil organic acid, metal wherein are selected from has 2 or be higher than the metal of divalent and the metal more less than the ionization tendency of those an alkali metal salts; And
(C) the organic monoprotic acid of high boiling point; From system, remove the lower boiling organic acid of formation at elevated temperatures.
The composition that US-A-2490925 discloses a kind of Pest Control comprises the rosin Amine D of stabilization and is scattered in coordination covalency metal-salt in kerosene, gasoline, benzene, ethanol, acetone, water or the turpentine wood oil.It is effective especially that said composition is claimed as a kind of sterilant.Said composition can add in the ocean coating of the dehydroabietylamine coordination compound that contains neutralized verdigris.
It wherein is the marine anti-pollution poisoning agent of the straight aliphatic primary amine of long-chain (12 to 18 carbon atom) or its salt that JP-A-54-64633 discloses a kind of.JP-A-54-110322 has disclosed some long-chain (12 to 18 carbon atom) linear aliphatic secondary amine and quaternary amine as the marine anti-pollution poisoning agent.
US-A-4675051 discloses a kind of marine antifouling coating, and it progressively dissolves in seawater and comprises a kind of by the binding agent of rosin with the resin formation of the aliphatic polyamines reaction generation that contains at least a primary amine or secondary amine group.
According to a kind of antifouling composition of the present invention, to contain a kind of marine organisms poisoning agent and comprise a kind of hydrolytic resin as binding agent, it has at least one following structural formula end group and is undertaken on resin at least one side chain: X-(O-M-R)
x, X represents in the formula:
Metal, X that M represents to be at least divalent represent 1 or 2, and R represents the univalent organic acid residue.This coating composition contains a kind of non-volatile basically amine that reduces hydrolytic resin binder solution viscosity.
Metal M in hydrolytic resin is each family: I b(such as Cu below being selected from the periodictable as an example), II a(is as Ca, Ba), II b(is as Zn, Cd), and III a(such as Sc, Y), III b(is as Al, and In), IV a(is as Ti, Zr), IV b(is as Sn, Pb, Si), V a(such as V, Nb), VI a(is as Cr, Mo, W), VI b(is as Se, Te), VII a(as: Mn) and VIII (as: Fe, Co, Ni) as an example, preferable metal M is Cu, Zn, Ni, Co or the Mn of divalence, is that better metal is Cu and Zn under 1 the situation at X.
Connecting X preferably is
Connect.As an example, hydrolytic resin can be produced by the EP-A-342276 method, by containing the resin of acid groups, preferably for containing resin and lower boiling organic acid metal-salt and high boiling organic monoprotic acid prepared in reaction of carboxylic acid.
The basic resin that contains acid groups preferably is 240 to 600 normal carboxylic acid functions' a polymkeric substance.Preferable acid function polymkeric substance is one or more alkene unsaturated acid or acid anhydrides, for example: the addition copolymer of vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, fumaric acid, itaconicacid or itaconicacid acid anhydride, vinyl benzoic acid (for example: right-vinyl benzoic acid), 3-butenoic acid or β-carboxyl-ethyl propylene acid esters or methacrylic ester and at least a alkene unsaturated comonomer.Methacrylic acid or acrylic acid multipolymer are preferable.[it is 14.3 to 35.8%(weight that preferable 240 to 600 equivalent is equivalent to acrylic acid content) and the methacrylic acid content be 16.7 to 41.7%(weight)].As an example, the preferable monomer with one or more comonomers (this comonomer and acid groups do not react) copolymerization is the ester of acrylic or methacrylic acid, such as: methyl acrylate, methyl methacrylate, ethyl propenoate, butyl acrylate or methacrylic acid 2-ethylhexyl, vinylbenzene, vinyl cyanide, vinyl-acetic ester, vinyl butyrate, vinylchlorid or vinyl pyridine.Ter-polymers may be for example preferable: methyl methacrylate or Jia Jibingxisuanyizhi, they trend towards forming a dura mater especially can be used on acrylate conjugated such as: ethyl propenoate or at moieties be 3 to 8 carbon atoms alkyl acrylate as: butyl acrylate, they help to form than the softish film.This class acid polymer preferably has 1,000 to 100,000 molecular weight.The equivalent of acid polymer (calculating with acid groups) 300 to 400 be the best, is equivalent to sour about 20 to the 30%(weight of acrylic or methacrylic) content.
Another kind of carboxylic acid function's polymkeric substance is a Synolac.
Another kind of acid function polymkeric substance is for containing the polymkeric substance of sulfonic group, phosphonate group or phosphoric acid (acid or phosphoric acid salt) group, they also can preferably be present in the addition polymer if adopt another kind of acid groups, as an example, the addition copolymer of the undersaturated phosphonic acids of a kind of alkylene, sulfuric acid or phosphoric acid.The example of the undersaturated acid of this class is vinyl phosphonate, styryl phosphonic acid, 2-aromatic amide propane phosphonic acid, ethylidene 1,1-di 2 ethylhexyl phosphonic acid, hydroxyethyl vinylformic acid phosplate, vinyl sulfuric acid, 2-aromatic amide-2-methylpropane sulfuric acid, methacrylic sulfuric acid and vinylbenzene sulfuric acid.The polymkeric substance that contains strong acid group such as sulfate group can have higher equivalent, as an example, can preferably be 1000 to 2000 in 500 to 5000 scope.
The monobasic organic acid residue R that is attached at hydrolytic resin is preferably for being selected from:
R in the formula
1Expression is by the organic residue of carbon atom banded unit price.This R
1Also can be expressed as an amino.
When adopting the method for EP-A-342276, with the metal-salt of matrix resin and high boiling point acid-respons be metal M and a kind of higher boil organic acid such as the salt of acetate or propionic acid.The residue R of this high boiling point acid RH is attached in the hydrolytic resin, and it has the boiling point high at least 20 ℃ than higher boil organic acid.This high boiling point acid RH can be carboxylic acid, sulfuric acid, thiocarboxylic acid, thiono carboxylic acid, carboxylamine, thiocarbamate, thion carboxylamine, dithionic acid or dithiocarbamic acid.Preferably, sour RH is a carboxylic acid, best for to have the aliphatic carboxylic acid that at least 8 carbon atoms are 12 to 20 carbon atoms as an example, for example: month good acid, stearic acid, oleic acid, linolic acid, ricinolic acid or 12-oxystearic acid; Another kind of carboxylic acid comprises that phenylformic acid, Whitfield's ointment, nitrobenzoic acid, Mono Chloro Acetic Acid, dichloro acetic acid or chlorinated benzene formic acid, this acid can be that mixture such as: the blended aliphatic carboxylic acid of carboxylic acid is with naphthenic acid or a kind ofly the alkanecarboxylic acid of side chain is arranged or from natural fat or oily deutero-acids form of mixtures sellers.Another class acid comprises that toluenesulphonic acids beta-naphthalenesulfonic-acid, right-chlorobenzenesulfonic acid, Methyl disulfide are for chloro formic acid and diethyldithiocar bamic acid.
This base resin, metal-salt and high boiling point acid are usually above the boiling point of lower boiling acid but be lower than the boiling point reaction down of high boiling point acid, to form hydrolytic resin.Reaction is preferably at organic solvent, as such as: the hydrocarbon of dimethylbenzene or Three methyl Benzene, such as: methyl isoamyl ketone or such as: carry out in the ester of butylacetate, ethoxyethyl acetate(EA) or acetate methoxyl group propyl ester.
The amine that is used for coating composition is essentially nonvolatile amine under envrionment temperature (20 ℃) and normal pressure.Preferably, it has at least 200 ℃ boiling point, and the best is at least 250 ℃.Should be by preferably being monoamine and being primary amine preferably, although also can adopt secondary amine and tertiary amine.This amine comprises that preferably at least one organic group contains at least 10 carbon atoms, more preferably contains 12 to 20 carbon atoms.Usually this class amine has the toxic advantage of marine organisms.This amine can be with the diterpene deutero-amine of following formula as an example:
R in the formula
1For from diterpene deutero-univalence hydrocarbyl and R
2And R
3For separately independently hydrogen, have the alkyl of 1 to 18 carbon atom or have the aryl of 6 to 12 carbon atoms.This preferable class amine is from the rosin deutero-.From rosin deutero-primary amine is dehydroabietylamine, and commercial with " rosin Amine D D " sale, its primary structure is:
Corresponding secondary amine or quaternary amine can adopt N-methyl or the N of rosin Amine D D, N-dimethyl derivative as an example.The diterpene amine is effective marine organisms poisoning agent.Another kind of amine is the aliphatic amine that contains the organic group of 12 to 20 carbon atoms, as an example as straight chained alkyl or alkenyl primary amine such as lauryl amine, hexadecylamine, octadecylamine or oleyl amine or be present in the aliphatic group deutero-amine of natural fat and oils certainly, such as: the mixture of beef tallow amine or hydrogenated butter amine or theobroma oil amine (cocoa amine) or corresponding secondary amine or quaternary amine such as N-methyl lauryl amine or N, N-dimethyl cocoa amine.Long chain aliphatic amine with 12 to 16 carbon atoms is very effective marine organisms poisoning agent.The another kind of amine that can adopt be aralkylamine such as those commercial sales as: the amine that " Phen-alkamines " or hydroxyl replace such as trolamine or diethanolamine.
Antifouling coating composition is preferably used at a kind of solution in organic solvent, example as solvent, such as: the hydro carbons of dimethylbenzene or petroleum solvent, the ketone of mibk, methyl isoamyl ketone, just-butanols, ethoxy ethanol or the alcohols of methoxypropanol or the ester class of butylacetate, ethoxyethyl acetate(EA) or acetate methoxyl group propyl ester.When the hydrolytic resin binding agent is when preparing in a kind of organic solvent, resin solution directly can be used in the coating of preparation.It can further at random dilute with solvent, and preferably this solvent is selected from above-mentioned listed.
Non-volatile amine have reduce hydrolytic resin solution as above-mentioned listed organic solvent in the advantage of viscosity.Believe that this amine to small part and the metal M in hydrolytic resin forms coordination compound.Metal M in coordination compound may with coordination bonding as the amine of ligand and anionic both, as an example, as: a carboxylate anion plays the R of organic acid residue effect.When forming the formation thing of colored hydrolytic resin solution coordination compound, these metals can see colour-change.As an example, the solution when metal M in hydrolytic resin is copper is green usually when not having amine, becomes blueness when adding amine.This amine can reduce the viscosity of hydrolytic resin solution up to reducing by 3/4.Hydrolytic resin solution is too sticking owing to there is not amine to be difficult to form the coating that can spray, so this amine can increase the resin content of hydrolytic resin solution as the base-material of hydrolytic resin solution.As an example, this amine can add to and have 30 to 35%(volumes) the hydrolytic resin solution of resin content in produce its viscosity be equal to have 25 to 30%(volumes) the solution of viscosity of the hydrolytic resin solution that does not have amine of resin content.In addition, since amine be non-volatile it also can directly improve a non-volatile matter content of coating composition.Recently in various coating compositions, be forced to adopt the content that reduces the volatilization organic solvent.
In coating composition hydrolytic resin to the ratio of amine preferably from 98: 2 to 10: the 90(volume), best, for from 90: 10 to 30: 70.The amine that does not have a film forming properties with no more than 40%(based on polymkeric substance and the two weight of amine) for preferable, otherwise, if desired,, can use with higher ratio such as the amine that film forming properties is arranged that the diterpene derivative is such.In addition, can adopt more than one amine, for example: diterpene amine can be reinstated with long chain aliphatic amine one.
If when marine organisms were the amine of poisoning agent, the coating composition of generation comprised hydrolytic resin and amine, can be used as transparent antifouling paint or can be used as colored coating with a kind of.If metal M is to the toxic metal of marine organisms in hydrolytic resin, as: copper, it can increase the ocean poisoning performance of coating, because the metal content of hydrolytic resin only is 10 to 15%(weight) but its effect may be big not enough.
If adopt the amine of non-poisoning, this coating composition should contain the marine organisms poisoning agent.It is preferable that coating contains pigment, if the pigment that adopts is a kind of poisoning agent pigment, this class pigment can have the similar function of marine organisms poisoning agent.
Amine is before other coating component adds, and preferably with the pre-mixing of hydrolytic resin binding agent, the hydrolytic resin binder solution also can mix with amine and pigment simultaneously.For example: hydrolytic resin solution and amine can adopt traditional coating method to mix with pigment that a kind of to have pigment volume concentration (PVC) be 25 to 55% composition to provide.Preferable pigment be a kind of have in seawater solubleness for from 0.5 to 100, be 1 to 10ppm(weight best) dissolved pigment abstemiously, preferably be a kind of metallic pigment.Best pigment is copper or zn cpds.For example: Red copper oxide, cuprous thiocyanate, zinc oxide, ziram, zinc diethyldithiocarbamate, ethylenebis (thiocarbamate) is cuprous and ethylenebis (dithiocarbamic acid) zinc.These copper and zn cpds are dissolved pigment abstemiously, also are a kind of marine organisms poisoning agent usually.This is metallic pigment of dissolved and the water miscible metallic compound of seawater reaction generation abstemiously, makes pigment material and the discontinuous coating surface that remains in.Also can adopt the mixture of dissolved pigment temperately, for example: Red copper oxide, cuprous thiocyanate or ethylenebis (dithiocarbamic acid) zinc, they are poisoning agent pigment efficiently, also can with a kind of as poisoning agent than poor efficiency but dissolve in seawater faster that zinc oxide mixes use.
This coating composition additionally or alternatively can contain with seawater nonreactive and may be at the undissolved pigment of seawater camber (solubleness is lower than 0.5ppm) such as titanium dioxide or ferric oxide or a kind of pigment dyestuff such as phthalocyanine pigment.The undissolved pigment of this class height preferably adopts and is less than 40%(weight) the total pigment component of coating based, be less than 20%(weight best).
This antifouling paint has a kind of nonmetallic marine organisms poisoning agent simultaneously, for example: tetramethyl-thiuram disulfide, methylene-bis (isocyanic ester), Captem are the isothiazolones or the 2-methylthio group-uncle 4--Ding amino-6-cyclopropylamino-sym-triazine of the replacement that discloses as an example as at GB1575226.
Below by execute the example the present invention is further illustrated.Embodiment 1 to 4
Based on the hydrolytic resin of the Sipacril 2739OF of acrylate and methacrylic ester dimethylbenzene at 4: 1: the solution A 28.9%(volume of butanols mixture), the side direction carboxyl of methacrylic acid wherein is converted into:
Group, the R in the formula
1Be high boiling point aliphatic carboxylic acid (naphthenic acid or analogue) deutero-, the ratio shown in the following table 1 is mixed with rosin Amine D D.The blending ratio that provides is, hydrolytic resin to rosin Amine D D(on dry basis) volume ratio.This green resin solution and colourless amine form a kind of blue solution, in this blueness of 40: 60 blending ratios (embodiment 3) for the denseest.
Table 1
Embodiment blending ratio solid content (volume) % viscosity mpa s
（A） 100∶0 28.9 240
1 80∶20 33.7 90
2 80∶40 40.4 90
3 40∶80 50.4 190
4 20∶80 67.0 190
As shown in table 1, the adding of rosin Amine D D reduces the viscosity (this is higher than the thick liquid resin of 1000mPas rosin Amine D D as viscosity) of hydrolytic resin solution.The product of embodiment 1 to 4 can be used as transparent antifouling varnish.In addition, they can with pigment, for example known poisoning agent pigment such as the Red copper oxide that is used in the antifouling paint, cuprous thiocyanate or ethylenebis (dithiocarbamic acid) zinc mixes.
Embodiment 5 to 12
Adopt two kinds of different hydrolytic resin solution to repeat the method for embodiment 1 to 4, each is the acrylic resin that contains following form side direction group:
Mixed viscosity is as shown in the table 2.The hydrolytic resin solution B of embodiment 5 to 8 has the 27.6%(volume) solids content, and the solution C of embodiment 9 to 12 has the 29.5%(volume) solids content.
Table 2
Embodiment blending ratio solid content (volume) % viscosity mpa s
（B） 100∶0 27.8 240
5 80∶20 32.3 100
6 60∶40 38.9 100
7 40∶60 48.8 250
8 20∶80 86.8 290
（D） 100∶0 29.5 360
9 80∶20 34.3 110
10 60∶40 41.0 120
11 40∶60 51.1 180
12 20∶80 67.6 280
Embodiment 13 to 21
In a high speed dispersion device, by traditional coating hybrid technology mixed hydrolysis resin solution (above-mentioned A, B or C), pigment and rosin Amine D D to be formed on the coating composition shown in the table 3 (quantity of composition is represented with weight %).
The coating of embodiment 13 to 21 used make steel plate priming paint and be immersed in the intensive geographic seawater of marine biological polution.Flood after 12 months, they prevent algae and asnimal pollution, and avirulent contrast plate shows serious pollution.
The coating of embodiment 19,20 and 21 is applied to test cover plate one side of underwater oil tank shell.After the torrid areas was through 11 months, this test cover plate is not algal suspension and asnimal pollution basically, and the contiguous cover plate that is not coated with antifouling paint is subjected to severe contamination.
Claims (13)
1, a kind of antifouling paint compositions is characterized in that containing the detailed biotoxin in a kind of sea and kills agent and comprise a kind of hydrolytic resin as binding agent, and it has at least one following structural formula end group and is undertaken at least one chain :-X-(O-M-R) x, and X represents in the formula:
Metal, X that M represents to be at least divalent represent 1 or 2, and R represents the monobasic organic acid residue.This coating composition contains a kind of non-volatile basically amine.
2, antifouling paint compositions as claimed in claim 1 is characterized in that, this hydrolytic resin is that X represents
Acid equivalent be the hydrolytic resin of 240 to 600 carboxylic acid function's polymer-derived.
3, as claimed in claim 1 or 2ly spin dirty coating composition, it is characterized in that metal M is that copper or zinc and x are 1.
4, antifouling paint compositions as claimed in claim 1 is characterized in that monobasic organic acid residue R is for being selected from:
R in the formula
1The organic residue of unit price that expression connects by carbon atom.
5, antifouling paint compositions as claimed in claim 4 is characterized in that monobasic organic acid residue R is the residue that the aliphatic carboxylic acid of at least 8 carbon atoms is arranged.
6, antifouling paint compositions as claimed in claim 1 is characterized in that a non-basically volatilization amine comprises that at least one organic group has the amine of at least 10 carbon atoms.
7, antifouling paint compositions as claimed in claim 6 is characterized in that described organic group is for having the organic group of 10 carbon atoms at least from the diterpene deutero-.
8, antifouling paint compositions as claimed in claim 6 is characterized in that described non-volatile basically amine is the fatty amine that contains the organic group of 12 to 20 carbon atoms.
9, antifouling paint compositions as claimed in claim 1, it is characterized in that in coating composition hydrolytic resin to the ratio of amine for from 90: 10 to 30: the 70(volume).
10,, it is characterized in that described amine exists with the coordination compound as ligand and metal M at least in part in hydrolytic resin as claim 1,2 or 4 to 9 described antifouling paint compositions.
11, as claim 1,2 or 4 to 9 described antifouling paint compositions, the pigment that it is characterized in that comprising is for having in seawater from 0.5 to 100ppm(weight) copper of solubleness or the pigment of zn cpds.
12, a kind of preparation comprises and contains a kind of marine organisms poisoning agent and comprise a kind of hydrolytic resin as binding agent, and it has at least one following structural formula end group and is undertaken at least one side chain: X-(O-M-R)
x, X represents in the formula:
Metal, x that M represents to be at least divalent represent 1 or 2, and R represents the method for the antifouling paint compositions of monobasic organic acid residue, it is characterized in that non-volatile amine basically is combined in the said composition.
13, method as claimed in claim 12 is characterized in that this amine and metal M form coordination compound in hydrolytic resin.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB909008053A GB9008053D0 (en) | 1990-04-10 | 1990-04-10 | Coating compositions |
| GB9008053.2 | 1990-04-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1055940A true CN1055940A (en) | 1991-11-06 |
Family
ID=10674173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91102406 Pending CN1055940A (en) | 1990-04-10 | 1991-04-10 | Antifouling paint compositions |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0530205B1 (en) |
| JP (1) | JPH05507947A (en) |
| CN (1) | CN1055940A (en) |
| DE (1) | DE69106359T2 (en) |
| DK (1) | DK0530205T3 (en) |
| ES (1) | ES2067228T3 (en) |
| GB (1) | GB9008053D0 (en) |
| GR (1) | GR3015104T3 (en) |
| PT (1) | PT97319B (en) |
| WO (1) | WO1991015546A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043240C (en) * | 1991-08-15 | 1999-05-05 | 永记造漆工业股份有限公司 | Self-abrasion anti-foul paint compound |
| CN1312238C (en) * | 2003-07-08 | 2007-04-25 | 贵州慧博科技开发有限公司 | Capsaicin self-polishing antifouling paint and its preparation method |
| CN100376644C (en) * | 2000-03-28 | 2008-03-26 | 日本油漆株式会社 | Antifouling coating |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5637745A (en) * | 1995-01-30 | 1997-06-10 | Elf Atochem North America, Inc. | Organometallic compounds and polymers made therefrom |
| KR100430841B1 (en) * | 1995-12-30 | 2005-01-10 | 고려화학 주식회사 | Antifouling paint composition containing self-polishing binder containing half-ester or half-amide having at least one ether group at terminal of side chain of polymer |
| KR19990081985A (en) * | 1996-01-26 | 1999-11-15 | 가마쿠라 아키오 | Triphenylborane-rosin amine addition compound and use thereof |
| KR100728479B1 (en) * | 1999-01-20 | 2007-06-13 | 아크조 노벨 엔.브이. | Antifouling paint |
| EP1036786A1 (en) * | 1999-03-16 | 2000-09-20 | Bayer Aktiengesellschaft | Rosin amine anti-fouling agents |
| JP4812947B2 (en) * | 2001-02-21 | 2011-11-09 | 日本ペイント株式会社 | High solid antifouling paint |
| JP2002294101A (en) * | 2001-03-28 | 2002-10-09 | Nippon Paint Co Ltd | Resin composition, method for manufacturing boronic polymer, and antifouling coating material |
| EP1308484A1 (en) | 2001-10-30 | 2003-05-07 | Sigma Coatings B.V. | Use of silylesters of rosin in self-polishing antifouling paints |
| NO328137B1 (en) * | 2001-12-26 | 2009-12-14 | Nippon Paint Co Ltd | Acrylic resin and anti-fouling coatings |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0764985B2 (en) * | 1985-05-17 | 1995-07-12 | 日本ペイント株式会社 | Metal-containing resin composition |
| JPH0667975B2 (en) * | 1986-11-17 | 1994-08-31 | 日本ペイント株式会社 | Method for producing resin for metal-containing paint |
-
1990
- 1990-04-10 GB GB909008053A patent/GB9008053D0/en active Pending
-
1991
- 1991-04-09 ES ES91907604T patent/ES2067228T3/en not_active Expired - Lifetime
- 1991-04-09 DK DK91907604T patent/DK0530205T3/en active
- 1991-04-09 EP EP91907604A patent/EP0530205B1/en not_active Expired - Lifetime
- 1991-04-09 DE DE69106359T patent/DE69106359T2/en not_active Expired - Fee Related
- 1991-04-09 WO PCT/GB1991/000561 patent/WO1991015546A1/en active IP Right Grant
- 1991-04-09 JP JP91506991A patent/JPH05507947A/en active Pending
- 1991-04-10 CN CN 91102406 patent/CN1055940A/en active Pending
- 1991-04-10 PT PT9731991A patent/PT97319B/en not_active IP Right Cessation
-
1995
- 1995-02-17 GR GR950400322T patent/GR3015104T3/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043240C (en) * | 1991-08-15 | 1999-05-05 | 永记造漆工业股份有限公司 | Self-abrasion anti-foul paint compound |
| CN100376644C (en) * | 2000-03-28 | 2008-03-26 | 日本油漆株式会社 | Antifouling coating |
| CN1312238C (en) * | 2003-07-08 | 2007-04-25 | 贵州慧博科技开发有限公司 | Capsaicin self-polishing antifouling paint and its preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0530205B1 (en) | 1994-12-28 |
| EP0530205A1 (en) | 1993-03-10 |
| PT97319A (en) | 1991-12-31 |
| PT97319B (en) | 1998-08-31 |
| WO1991015546A1 (en) | 1991-10-17 |
| GB9008053D0 (en) | 1990-06-06 |
| DE69106359T2 (en) | 1995-06-22 |
| JPH05507947A (en) | 1993-11-11 |
| GR3015104T3 (en) | 1995-05-31 |
| ES2067228T3 (en) | 1995-03-16 |
| DE69106359D1 (en) | 1995-02-09 |
| DK0530205T3 (en) | 1995-06-06 |
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